Siloxane polymer composition, method of forming a pattern using the same, and method of manufacturing a semiconductor using the same

Abstract

A siloxane polymer composition includes an organic solvent in an amount of about 93 percent by weight to about 98 percent by weight, based on a total weight of the siloxane polymer composition, and a siloxane complex in an amount of about 2 percent by weight to about 7 percent by weight, based on the total weight of the siloxane polymer composition, the siloxane complex including a siloxane polymer with an introduced carboxylic acid and being represented by Formula 1 below, wherein each of R 1 , R 2 R 3 , and R 4 independently represents H, OH, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 or C 5 H 11 , R′ represents CH 2 , C 2 H 4 , C 3 H 6 , C 4 H 8 , C 5 H 10 or C 6 H 12 , and n represents a positive integer so the siloxane polymer of the siloxane complex has a number average molecular weight of about 4,000 to about 5,000.

1. A method of forming a pattern, comprising:
 forming an opening through an insulation layer on a substrate, the opening partially exposing the substrate; 
 forming a conductive layer in the opening and on the insulation layer; 
 forming a siloxane layer on the conductive layer to fill the opening, the siloxane layer including
 an organic solvent in an amount of about 93 percent by weight to about 98 percent by weight, based on a total weight of the siloxane layer, and 
 a siloxane complex in an amount of about 2 percent by weight to about 7 percent by weight, based on the total weight of the siloxane layer, the siloxane complex including a siloxane polymer with an introduced carboxylic acid and being represented by Formula 1 below, 
 
 
     
       
         
         
             
             
         
       
       
         wherein each of R 1 , R 2  R 3 , and R 4  independently represents H, OH, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9  or C 5 H 11 , R′ represents CH 2 , C 2 H 4 , C 3 H 6 , C 4 H 8 , C 5 H 10  or C 6 H 12 , and n represents a positive integer so the siloxane polymer of the siloxane complex has a number average molecular weight of about 4,000 to about 5,000; 
       
       forming a siloxane pattern in the opening by partially removing the siloxane layer; and 
       forming a conductive layer pattern by etching the conductive layer using the siloxane pattern as an etching mask. 
     
   
   
     2. The method as claimed in  claim 1 , further comprising:
 forming the conductive layer on the substrate, sidewalls of the opening, and the insulation layer; 
 forming a preliminary siloxane layer on the conductive layer to fill the opening; 
 forming the siloxane layer by hardening the preliminary siloxane layer; and 
 removing the siloxane layer pattern and the insulation layer after forming the conductive layer pattern. 
 
   
   
     3. The method as claimed in  claim 2 , wherein hardening the preliminary siloxane layer includes a baking process performed at a temperature of about 90° C. to about 110° C. 
   
   
     4. The method as claimed in  claim 2 , wherein the siloxane pattern and the insulation layer are removed simultaneously. 
   
   
     5. The method as claimed in  claim 4 , wherein the siloxane pattern and the insulation layer are removed using an etching solution including a hydrogen fluoride solution, an ammonium fluoride solution, and deionized water. 
   
   
     6. The method as claimed in  claim 1 , wherein the siloxane pattern is formed by partially removing the siloxane layer using a tetramethyl ammonium hydroxide (TMAH) solution. 
   
   
     7. A method of manufacturing a semiconductor device, comprising:
 forming a mold layer on a substrate with a conductive structure, the mold layer having an opening exposing the conductive structure; 
 conformally forming a conductive layer on the conductive structure, sidewalls of the opening, and the mold layer; 
 forming a siloxane layer on the conductive layer to fill the opening, the siloxane layer including
 an organic solvent in an amount of about 93 percent by weight to about 98 percent by weight, based on a total weight of the siloxane layer, and 
 a siloxane complex in an amount of about 2 percent by weight to about 7 percent by weight, based on the total weight of the siloxane layer, the siloxane complex including a siloxane polymer with an introduced carboxylic acid and being represented by Formula 1 below, 
 
 
     
       
         
         
             
             
         
       
       
         wherein each of R 1 , R 2  R 3 , and R 4  independently represents H, OH, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9  or C 5 H 11 , R′ represents CH 2 , C 2 H 4 , C 3 H 6 , C 4 H 8 , C 5 H 10  or C 6 H 12 , and n represents a positive integer so the siloxane polymer of the siloxane complex has a number average molecular weight of about 4,000 to about 5,000; 
       
       forming a siloxane pattern in the opening by partially removing the siloxane layer using a TMAH solution; 
       forming a lower electrode by partially removing the conductive layer from the mold layer by using the siloxane pattern as an etching mask; 
       removing the siloxane pattern and the mold layer; 
       forming a dielectric layer on the lower electrode; and 
       forming an upper electrode on the dielectric layer. 
     
   
   
     8. The method as claimed in  claim 7 , wherein the siloxane layer is formed by baking a composition of the siloxane complex and organic solvent at a temperature of about 90° C. to about 110° C., and the siloxane polymer of the siloxane complex is formed on a crosslinking product of a siloxane compound. 
   
   
     9. The method as claimed in  claim 7 , wherein the siloxane complex is obtained by reacting carboxylic acid chloride (R′—Cl—COOH) with a hydroxyl group of a siloxane polymer having a number average molecular weight of about 4,000 to about 5,000, and is represented by Formula 2 below, 
     
       
         
         
             
             
         
       
       wherein each of R 1 , R 2  R 3 , and R 4  independently represents H, OH, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9  or C 5 H 11 , R′ represents CH 2 , C 2 H 4 , C 3 H 6 , C 4 H 8 , C 5 H 10  or C 6 H 12 , and n represents a positive integer so the siloxane polymer has the number average molecular weight of about 4,000 to about 5,000. 
     
   
   
     10. The method as claimed in  claim 7 , wherein the siloxane complex has a PDI of about 1.3 to about 1.8. 
   
   
     11. The method as claimed in  claim 7 , wherein the siloxane complex is represented by Formula 4 below, 
     
       
         
         
             
             
         
       
       wherein each of R 1 , R 2  R 3 , and R 4  independently represents H, OH, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9  or C 5 H 11 , and n represents a positive integer so the siloxane polymer has the number average molecular weight of about 4,000 to about 5,000. 
     
   
   
     12. The method as claimed in  claim 11 , wherein R′ represents CH 2 , C 2 H 4 , C 3 H 6 , C 4 H 8 , C 5 H 10  or C 6 H 12 . 
   
   
     13. The method as claimed in  claim 7 , wherein the siloxane pattern and the mold layer are removed simultaneously. 
   
   
     14. The method as claimed in  claim 13 , wherein the siloxane pattern and the mold layer are removed using an etching solution including a hydrogen fluoride solution, an ammonium fluoride solution, and deionized water.